EP0010346A1 - Polyoléfines stabilisées contre la lumière et stabilisant à la lummière pour de telles compositions - Google Patents

Polyoléfines stabilisées contre la lumière et stabilisant à la lummière pour de telles compositions Download PDF

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Publication number
EP0010346A1
EP0010346A1 EP79301686A EP79301686A EP0010346A1 EP 0010346 A1 EP0010346 A1 EP 0010346A1 EP 79301686 A EP79301686 A EP 79301686A EP 79301686 A EP79301686 A EP 79301686A EP 0010346 A1 EP0010346 A1 EP 0010346A1
Authority
EP
European Patent Office
Prior art keywords
light
light stabilizer
butyl
alkyl
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP79301686A
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German (de)
English (en)
Other versions
EP0010346B1 (fr
Inventor
Joseph Anthony Stretanski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wyeth Holdings LLC
Original Assignee
American Cyanamid Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by American Cyanamid Co filed Critical American Cyanamid Co
Priority to AT79301686T priority Critical patent/ATE4993T1/de
Publication of EP0010346A1 publication Critical patent/EP0010346A1/fr
Application granted granted Critical
Publication of EP0010346B1 publication Critical patent/EP0010346B1/fr
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/13Phenols; Phenolates
    • C08K5/134Phenols containing ester groups
    • C08K5/1345Carboxylic esters of phenolcarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/13Phenols; Phenolates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/527Cyclic esters

Definitions

  • the present invention relates in general to the stabilization of poly-a-olefins against light-induced deterioration and, in particular, to polypropylene compositions so stabilized by the incorporation therein of an effective light stabilizing amount of a combination of (a) n-hexadecyl 3,5-di-t.butyl-4-hydroxybenzoate and (b) a dialkyl pentaerythrityl diphosphite.
  • a benzophenone or benzotriazole may be added for improved stability.
  • alkyl esters nor the aryl esters of 3,5-di-t.butyl-4-hydroxybenzoic acid are, when used alone, completely satisfactory light stabilizers for .polyolefins, although it is believed that the alkyl esters, particularly the higher alkyl (C 8 -C 20 ), are somewhat superior to the aryl esters.
  • the present invention provides light stabilizer compositions, which exhibit enhanced light stability in poly- ⁇ -olefins, comprising a combination of (a) n-hexadecyl 3,5-di-t.butyl-4-hydroxybenzoate and (b) a dialkyl pentaery- thrityl diphosphite compound, represented by the formula: wherein R is an alkyl group containing from about 8 to 20 carbon atoms. Further enhancement of the light stability arises from adding to the above combination a benzophenone or benzotriazole compounds
  • the invention provides light stabilizer compositions, as defined, and light stabilized poly-a-olefin co positions containing an effective light stabilizing amount of the light stabilizer composition, as well as a method for stabilizing poly-a-olefins against light-induced degradation by the incorporation therein of an effective light stabilizing amount of the above-defined light stabilizer compositions.
  • compositions of the invention provide significantly enhanced light stability to poly-a-olefins, particularly polypropylene, over either component used alone at the same concentration, or over combinations of n-hexadecyl 3,5-di-t.butyl-4-hydroxybenzoate with other known phosphite esters, or over aryl esters of 3,5-di-t.butyl-4-hydroxybenzoic acid with known phosphites, including dialkyl pentaerythrityl diphosphites.
  • n-Hexadecyl 3,5-di-t.butyl-4-hydroxybenzoate is a known compound. It may be prepared in accordance with procedures described in U.S. Patent 3,681,431, for the preparation of the n-octadecyl ester, except that n-hexadecanol is used instead-of n-octadecanol.
  • dialkyl pentaerythrityl diphosphites are also known compounds and are described in U.S. Patent 3,205,250, particularly column 7, lines 25-43, and in Examples 9-13 therein.
  • the preferred dialkyl pentaerythrityl diphosphites contain C 8 -C 20 alkyl groups, and most preferably contain C 12 -C 20 alkyl groups, representative of which are diisodecyl pentaerythrityl diphosphite, distearyl pentaerythrityl diphosphite, dilauryl pentaerythrityl diphosphite, and the like.
  • Distearyl pentaerythrityl diphosphite available commercially as Weston 618 (Weston Chem. Co.) is the most preferred diphosphite.
  • effective stabilization of the polyolefin is achieved by the incorporation therein of about 0.1 to 2 percent by weight of the light stabilizer combination of the invention and preferably from about 0.25 to about 1 percent by weight.
  • the weight ratio of the n-hexadecyl ester of 3,5--di-t.butyl-4-hydroxybenzoic acid to the dialkyl pentaery- thrityl diphosphite in the light stabilizer combination will preferably be such as to minimize the amount of the phosphite ester. In general, however, effective weight ratios will vary between about 1:1 to about 5:1 (ester:phosphite).
  • the benzophenone or benzotriazole when used, are used in amounts of about 0.1 to 1 percent by weight.
  • the stabilizer composition of the invention may also contain a benzophenone or benzotriazole light stabilizer to provide further enhancement of activity.
  • the benzophenone or benzotriazole may be added in an amount of from about 0.1 to 1 percent by weight, based on the weight of the polymer, with the ratio of n-hexadecyl ester to benzophenone or benzotriazole being about 1/1 to 5/1.
  • Representative benzophenones include 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-n-hexyloxy- benzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy--4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, and the like; representative benzotriazoles include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert.butyl--2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole, 2-(3',5'--di-tert.butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert.octylphenyl)benzotriazole, 2-(3',5'-di-tert.amyl-2
  • the polyolefins stabilized in accordance with the invention are poly-a-olefins, particularly polypropylene, and include low and high density polyethylene, polybutylene, and copolymers of ethylene and propylene and ethylene and butylene, and the like.
  • the stabilizer composition may be incorporated into the polyolefin by any of the means well-known in the art for such purpose, including dry blending of the additive with the polyolefin in powder or granular form, followed by milling, Banbury mixing, molding, casting, etc.
  • the compositions may include other stabilizers, such as thermal processing anti oxidants, lubricants, fillers, pigments and dyes, antistatic agents, and the like.
  • thermal processing antioxidants which may be used alone or in combinations are used in conventional effective amounts, i.e. up to about 2 percent by weight.
  • Suitable compounds include such as:
  • Unstabilized powdered polypropylene (Profax 6401-Hercules; 100 parts by weight was dry blended with two thermal processing antioxidants (0.05 part by weight of 2,6-di-t. butyl-4-methyl phenol and 0.05 part by weight of n-octadecyl 3,5-di-t.butyl-4-hydroxyhydrocinnamate) 0.1 part by weight of calcium stearate, and the light stabilizers shown in the accompanying table.
  • the compositions were then extruded at a maximum extrusion temperature of 440°F and pelletized.
  • the pellets were then extruded into fibers at a maximum temperature of 485°F using a draw ratio of 7/1.
  • the fibers were exposed to a Xenon arc in a Weather-O-Meter and periodically tested for tensile (break) strength.
  • the data shown in the table represent the time in hours for the fiber to lose 50% of its original tensile (break) strength.
  • the data show the unexpected enhancement of light stabilization by the combination of the invention (d) over 'either component alone (b) and (c), as well as over the aryl ester alone (e) or in combination with distearyl pentaery- thrityl diphosphite (f).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP79301686A 1978-10-13 1979-08-17 Polyoléfines stabilisées contre la lumière et stabilisant à la lummière pour de telles compositions Expired EP0010346B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79301686T ATE4993T1 (de) 1978-10-13 1979-08-17 Gegen licht stabilisierte olefinpolymerisate und eine lichtstabilisator-mischung dafuer.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US951230 1978-10-13
US05/951,230 US4237042A (en) 1978-10-13 1978-10-13 Polyolefins stabilized against light-induced degradation

Publications (2)

Publication Number Publication Date
EP0010346A1 true EP0010346A1 (fr) 1980-04-30
EP0010346B1 EP0010346B1 (fr) 1983-10-12

Family

ID=25491454

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79301686A Expired EP0010346B1 (fr) 1978-10-13 1979-08-17 Polyoléfines stabilisées contre la lumière et stabilisant à la lummière pour de telles compositions

Country Status (8)

Country Link
US (1) US4237042A (fr)
EP (1) EP0010346B1 (fr)
JP (1) JPS5554339A (fr)
AT (1) ATE4993T1 (fr)
AU (1) AU526749B2 (fr)
BR (1) BR7906130A (fr)
CA (1) CA1111238A (fr)
DE (1) DE2966299D1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0048344A1 (fr) * 1980-09-19 1982-03-31 American Cyanamid Company Compositions polyoléfiniques stabilisées contenant l'oxyde de titane
EP0048562A1 (fr) * 1980-09-18 1982-03-31 Uniroyal, Inc. Combinaison de stabilisants pour matières organiques à base de dérivés d'oxamides phénoliques et de phosphites
EP0953596A2 (fr) * 1998-04-27 1999-11-03 Asahi Denka Kogyo Kabushiki Kaisha Matériau de garniture pour l' intérieur ou l'extérieur d' automobiles

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4670491A (en) * 1980-09-19 1987-06-02 American Cyanamid Company Stabilized titanium dioxide-pigmented polyolefin compositions
JPS57200455A (en) * 1981-06-05 1982-12-08 Tokuyama Soda Co Ltd Thermoplastic resin composition
JPS5884839A (ja) * 1981-11-17 1983-05-21 Mitsui Petrochem Ind Ltd 給水・給湯配管用ポリ‐1ブテン樹脂組成物
CA1200038A (fr) * 1982-01-28 1986-01-28 Elyse M. Lewis Polyethylene lineaire stabilise de faible densite
US5378747A (en) * 1992-12-28 1995-01-03 Phillips Petroleum Company Ethylene polymer compositions
EP1004621B1 (fr) * 1998-06-11 2004-09-15 Teijin Chemicals, Ltd. Stabilisateur anti-rayons gamma et composition polymere thermoplastique contenant ce stabilisateur
WO2003057772A2 (fr) * 2001-12-27 2003-07-17 Cytec Technology Corp. Olefines thermoplastiques stabilisees uv

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2106095A5 (fr) * 1970-08-26 1972-04-28 Ciba Geigy Ag
US3681431A (en) * 1970-02-06 1972-08-01 Ciba Geigy Corp N-OCTADECYL 3,5-DI-t-BUTYL-4-HYDROXYBENZOATE
BE849782A (fr) * 1976-12-23 1977-06-23 Compositions stabilisees a base de polymeres d'alpha-olefines
FR2389652A1 (fr) * 1977-05-06 1978-12-01 Borg Warner

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3039993A (en) * 1960-05-10 1962-06-19 Weston Chemical Corp Polyethylene stabilizers
US3205250A (en) * 1961-11-20 1965-09-07 Hooker Chemical Corp 3, 9-alkoxy and 3, 9-chloropropyl-2, 4, 8, 10-tetraoxa-3, 9-phosphospiro (6, 6) hendeanes
US3206431A (en) * 1964-09-15 1965-09-14 Shell Oil Co Thermoplastic polymers containing 3,5-dialkyl-4-hydroxybenzoic acid esters as u.v. stabilizers
CA962793A (en) 1970-02-27 1975-02-11 Paul J. Papillo Stabilized polyolefine composition
US4064100A (en) * 1975-07-22 1977-12-20 Weston Chemical Co., Inc. Friable distearyl pentaerythritol diphosphite

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3681431A (en) * 1970-02-06 1972-08-01 Ciba Geigy Corp N-OCTADECYL 3,5-DI-t-BUTYL-4-HYDROXYBENZOATE
FR2106095A5 (fr) * 1970-08-26 1972-04-28 Ciba Geigy Ag
BE849782A (fr) * 1976-12-23 1977-06-23 Compositions stabilisees a base de polymeres d'alpha-olefines
FR2389652A1 (fr) * 1977-05-06 1978-12-01 Borg Warner

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0048562A1 (fr) * 1980-09-18 1982-03-31 Uniroyal, Inc. Combinaison de stabilisants pour matières organiques à base de dérivés d'oxamides phénoliques et de phosphites
EP0048344A1 (fr) * 1980-09-19 1982-03-31 American Cyanamid Company Compositions polyoléfiniques stabilisées contenant l'oxyde de titane
EP0953596A2 (fr) * 1998-04-27 1999-11-03 Asahi Denka Kogyo Kabushiki Kaisha Matériau de garniture pour l' intérieur ou l'extérieur d' automobiles
EP0953596A3 (fr) * 1998-04-27 1999-12-15 Asahi Denka Kogyo Kabushiki Kaisha Matériau de garniture pour l' intérieur ou l'extérieur d' automobiles

Also Published As

Publication number Publication date
ATE4993T1 (de) 1983-10-15
JPS6210531B2 (fr) 1987-03-06
CA1111238A (fr) 1981-10-27
AU4998679A (en) 1980-04-17
JPS5554339A (en) 1980-04-21
US4237042A (en) 1980-12-02
DE2966299D1 (en) 1983-12-22
AU526749B2 (en) 1983-01-27
BR7906130A (pt) 1980-06-03
EP0010346B1 (fr) 1983-10-12

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